CN103265280A - Method for preparing YBCO (yttrium barium copper oxide) film by use of low-fluorine MOD (metal organic deposition) process - Google Patents
Method for preparing YBCO (yttrium barium copper oxide) film by use of low-fluorine MOD (metal organic deposition) process Download PDFInfo
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Abstract
The invention relates to a method for preparing a YBCO (yttrium barium copper oxide) film by use of a low-fluorine MOD (metal organic deposition) process. According to the method, by adding polyethyleneimine (PEI) into the mixed precursor liquid containing yttrium trifluoroacetate, barium trifluoroacetate and copper propionate, polyethyleneimine is subjected to complexation with metal ions through repeated rotary evaporation in the precursor liquid, the viscosity of the solution is controlled, and the stability of the solution is improved. By adjusting the dosage of an additive and adopting a one-step sintering process, a surface crack-free YBCO film with a biaxial structure and excellent grain orientation is successfully prepared through low-temperature thermal decomposition and high-temperature sintering. The film does not have cracks on the surface, the hole is tiny, and the thickness can reach 500-600nm; and under a condition of assuming the film thickness to be 200nm, the maximum critical current density Jc measured by a CRYOSCAN scanning induction critical current tester according to THEVA DUNUSCHICHTTECHNIK GMBH can reach 4.5MA/cm<2> (77K, 0T).
Description
Technical field
The present invention relates to the method that a kind of low fluorine MOD legal system is equipped with ybco film, belong to the high temperature superconducting materia preparing technical field.
Background technology
Coating conductor is the multilayered structure section bar material that is made of metal substrate, buffer layer, superconducting layer, protective layer etc., mainly contains first-generation Bi system and s-generation Y system.Compare the YBCO(yttrium barium copper oxide with Bi frenulum material) superconducting tape has higher irreversible and higher current load ability, can make band at the flexible metal substrate surface epitaxial growth film that contains buffer layer.Because narrow, the magnetic field lower critical current density height of critical temperature height, width of transition of YBCO band, people have produced greatly interest to the research of YBCO coating conductor in recent years, mainly can be applicable to the fields such as manufacturing of transmission, high-efficiency electric motor and the generator of military affairs, medical science and high-power electric current.
Preparing ybco film with the general physical method compares, metal organic deposit method (MOD) does not need vacuum system, and can accurately control the composition of precursor liquid, be easy to realize the deposition of large area film, effectively reducing industrial cost, is now for the preparation of one of main stream approach of YBCO coating conductor.Although the TFA-MOD method has plurality of advantages, when the single application thickness that traditional TFA-MOD legal system is equipped with ybco film surpassed 500 nm, film very easily cracked, hole, and critical current density is sharply descended.And thicker YBCO coating helps the electric current that makes the superconducting tape transmission bigger, thereby it is thicker and have a YBCO coating of certain critical current density to make rete as far as possible by single application or the mode that repeatedly applies.If each coating thickness is at 200-300 nm, just can obtains thickness and reach 1.5 μ m, surperficial uncracked ybco film (Chinese patent application number 200810240067.7) by applying for 5 times.Even select neodecanoic acid copper, different n-nonanoic acid copper, 2 ethyl hexanoic acid copper and copper naphthenate etc. as raw material, adopt low fluorine MOD legal system to be equipped with ybco film, single application thickness also only is 300 nm(Chinese patent Granted publication CN100392770C).
Adding that it is generally acknowledged additive helps the performance of ybco film to improve and viscosity controller, common have polyvinyl alcohol (PVA) (Chinese patent Granted publication CN102173777B), polyvinyl butyral acetal (PVB) (Chinese patent Granted publication CN101456726B), a polyvinylpyrrolidone (PVP) (Chinese patent Granted publication CN100415680C) etc., and performance is also uneven.People such as tight military defense are that raw material, water are solvent with nitrate, add additives polyvinyl alcohol, polyoxyethylene glycol and sucrose and prepare ybco film, and critical current density is about 1 MA/cm
2(77 K, self-fields) (Chinese patent Granted publication CN102173777B; Tight military defense, Zhang Chengxiao, Wang Pengfei etc. nitrate PAD method prepares YBCO superconducting thin film research [J] functional materials .2012,43 (8): 984-986.) fast.Other has the situation that adds the additive diethanolamine in precursor liquid, and the monolayer film thickness that makes can reach 1 μ m, generates and BaCO but still there is a small amount of a axialite grain
3Intermediate phase residual, the integral sintered time needs 10.5 hours (Chinese patent Granted publication CN101719399B; Tang Xiao, Suo Hongli, Ye Shuai, Liu Min, Wu Ziping, Zhou Meiling. low fluorine TFA-MOD technology prepares research [J] the Journal of Inorganic Materials .2010 of YBCO superconducting thick-film, 25 (9): 971-974.) fast.Although additive is early had report for the preparation of the method for ybco film, but adopt the resultant ybco film of above-mentioned additive to have thickness then to ftracture or problem such as performance is not good, single application thickness also is no more than 500 nm basically, does not have employing polymine (PEI) to be used for the report that low fluorine MOD legal system is equipped with ybco film as additive in addition as yet.
Summary of the invention
The object of the present invention is to provide a kind of low fluorine MOD legal system to be equipped with the method for ybco film, this method can effectively improve thickness and the critical current density of ybco film, can overcome surface crack and thickness problem that traditional TFA-MOD legal system is equipped with ybco film, it is low to have fluorine content, the characteristics that chemical stability is high.
For achieving the above object, the present invention adopts and add additive polymine (PEI) in the precursor liquid of trifluoroacetic acid yttrium, trifluoroacetic acid barium and propionic acid copper, by adjusting the consumption of additive, adopt a step sintering process, prepare excellent performance, ybco film that rete is thicker.Adopt following technical scheme preparation:
A. acetic acid yttrium and barium acetate are dissolved in methyl alcohol by the mol ratio of 1:2 and the trifluoroacetic acid of excessive 10 % mol ratios, adopt the Rotary Evaporators desolventizing, obtain the water white transparency colloidal liquid;
B. neutralized verdigris and propionic acid are dissolved in methyl alcohol in 1:4 ~ 6 in molar ratio, adopt the Rotary Evaporators desolventizing, obtain the green transparent colloid;
C. steps A is mixed by the mol ratio of Y:Ba:Cu=1:2:3 with the solution that B obtains, revolve steaming repeatedly under 85 ℃, obtain pure blue-greenish colour transparent colloid, the gel of gained adds methyl alcohol, stirs, and obtains the blue-greenish colour clear solution;
D. the polymine (PEI) with quality 0.2 ~ 1.0 g is dissolved in a certain amount of methyl alcohol, stirs, and obtains colourless transparent solution;
E. polymine-methanol solution that step D is obtained joins in the blue-greenish colour clear solution that step C makes, and both volume ratios are 1:2, revolve steaming under 85 ℃ repeatedly, and with the bubbling boiling phenomenon, obtain the mazarine transparent colloid;
F. in the mazarine transparent colloid that step e makes, add methyl alcohol, make the solution that metallic cation concentration is 1.5 mol/L;
G. the precursor liquid that step F is made is coated on the substrate by spin-coating method;
H. will adopt a step sintering process through the coated substrate of step G, experience low-temperature decomposition process, high-temperature heat treatment process and annealing process prepare ybco film.
The present invention adds polymine (PEI) in the precursor liquid that contains trifluoroacetic acid yttrium, trifluoroacetic acid barium and propionic acid copper, polymine is steamed and metal ion generation complexing through revolving repeatedly in precursor liquid, and the viscosity of control solution increases stability of solution.By adjusting the consumption of additive, adopt a step sintering process, through low temperature thermal decomposition and high temperature sintering, successfully prepare ybco film.Adopt the thickness of the ybco film that this method makes to reach 500 ~ 600 nm, the film surface flawless, hole is minimum, CRYOSCAN scanning induction critical current tester according to THEVA DUNUSCHICHTTECHNIK GMBH is under the condition of 200 nm at the supposition film thickness, records critical current density
JC can reach 4.5 MA/cm
2(77 K, 0 T).
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the ybco film of embodiment 1 preparation;
Fig. 2 is the thermal field emission scan electron microscope picture of the ybco film of embodiment 1 preparation;
Fig. 3 is the ybco film of embodiment 1 preparation
JThe c test shows figure;
Fig. 4 is the ybco film of embodiment 1 preparation
JC take off data figure.
Embodiment
The present invention is described in detail below in conjunction with embodiment:
Embodiment one
Concrete steps are as follows:
A. acetic acid yttrium and barium acetate are dissolved in methyl alcohol by the mol ratio of 1:2 and the trifluoroacetic acid of excessive 10 % mol ratios, adopt the Rotary Evaporators desolventizing, obtain the water white transparency colloidal liquid;
B. neutralized verdigris and propionic acid are dissolved in methyl alcohol in 1:4 ~ 6 in molar ratio, adopt the Rotary Evaporators desolventizing, obtain the green transparent colloid;
C. steps A is mixed by the mol ratio of Y:Ba:Cu=1:2:3 with the solution that B obtains, revolve steaming repeatedly under 85 ℃, obtain pure blue-greenish colour clear gel, the gel of gained adds methyl alcohol, stirs, and obtains the blue-greenish colour clear solution;
D. the polymine (PEI) that with quality is 0.5 g is dissolved in a certain amount of methyl alcohol, stirs, and obtains colourless transparent solution;
E. polymine-methanol solution that step D is obtained joins in the blue-greenish colour clear solution that step C makes, and both volume ratios are 1:2, revolve steaming under 85 ℃ repeatedly, and with the bubbling boiling phenomenon, obtain the mazarine transparent colloid;
F. in the mazarine transparent colloid that step e makes, add methyl alcohol, make the solution that metallic cation concentration is 1.5 mol/L.
G. the precursor liquid that step F is made is spin-coated on the LAO monocrystal chip with the speed of 5000 rpm/min, and the spin coating time is 40 s;
H. will be put in through the coated substrate of step G and place tube furnace on the quartz plate.At dried pure O
2Speed with 10 ℃/min under the atmosphere rises to 200 ℃ fast by room temperature, and the speed with 2 ℃/min rises to 365 ℃ by 200 ℃ again, and is incubated 10 min, and then atmosphere transfers wet O to
2, be warming up to 550 ℃ with the speed of 5 ℃/min.At 770 ℃ of sintering 90 min, wherein preceding 60 min are wet Ar/O with forerunner's noncrystal membrane
2Gas mixture atmosphere, back 30 min are for doing Ar/O
2Gas mixture atmosphere.At last at dried Ar/O
2When cooling to 525 ℃ in the gas mixture atmosphere, be changed to pure O
2, at 450 ℃ of insulation 60 min, make the YBCO oxygen uptake of cubic phase change the YBCO that quadrature has superconductivity mutually into, sample is at pure O subsequently
2Cool to room temperature with the furnace under the atmosphere.The integral sintered time is about 7.5 hours.
Show from the X ray collection of illustrative plates (Fig. 1) of the ybco film of the present embodiment preparation, ybco film c orientation obviously, each diffraction peak-to-peak is stronger, and assorted peak is few.Adopt field emission scanning electron microscope that the sample surfaces pattern is observed, the result shows the smooth flawless of YBCO thick film surface, no a axle orientation crystal grain (Fig. 2).CRYOSCAN scanning induction critical current tester according to THEVA DUNUSCHICHTTECHNIK GMBH is under the condition of 200 nm at the supposition film thickness, carries out the critical current density test of film.Can see that from the test pattern of Fig. 3 prepared ybco film has higher superconductivity,
JC can reach 4.5 MA/cm
2(77 K, 0 T) (Fig. 4), the actual (real) thickness of single application can reach 500-600 nm.
Claims (2)
1. one kind low fluorine MOD legal system is equipped with the method for ybco film, it is characterized in that this method has following processing step:
A. acetic acid yttrium and barium acetate are dissolved in methyl alcohol by the mol ratio of 1:2 and the trifluoroacetic acid of excessive 10 % mol ratios, adopt the Rotary Evaporators desolventizing, obtain the water white transparency colloidal liquid;
B. neutralized verdigris and propionic acid are dissolved in methyl alcohol in 1:4 ~ 6 in molar ratio, adopt the Rotary Evaporators desolventizing, obtain the green transparent colloid;
C. steps A is mixed by the mol ratio of Y:Ba:Cu=1:2:3 with the solution that B obtains, revolve steaming repeatedly under 85 ℃, obtain pure blue-greenish colour transparent colloid, the gel of gained adds methyl alcohol, stirs, and obtains the blue-greenish colour clear solution;
D. the polymine with quality 0.2 ~ 1.0 g is dissolved in a certain amount of methyl alcohol, stirs, and obtains colourless transparent solution;
E. polymine-methanol solution that step D is obtained joins in the blue-greenish colour clear solution that step C makes, and both volume ratios are 1:2, revolve steaming under 85 ℃ repeatedly, and with the bubbling boiling phenomenon, obtain the mazarine transparent colloid;
F. in the mazarine transparent colloid that step e makes, add methyl alcohol, make the solution that metallic cation concentration is 1.5 mol/L;
G. the precursor liquid that step F is made is coated on the substrate by spin-coating method;
H. will adopt a step sintering process through the coated substrate of step G, experience low-temperature decomposition process, high-temperature heat treatment process and annealing process prepare ybco film.
2. the method that is equipped with ybco film by the described low fluorine MOD legal system of claim 1, it is characterized in that described preparation method adopts polymine as additive, polymine is steamed and metal ion generation complexing, the viscosity of control solution when increasing stability of solution in precursor liquid through revolving repeatedly; By adjusting the consumption of additive, adopt a step sintering process, prepare the ybco film of excellent performance.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311641A (en) * | 2017-07-25 | 2017-11-03 | 东北大学 | A kind of method that step Technology for Heating Processing prepares boron doped YBCO superconducting film |
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| CN101501787A (en) * | 2006-07-17 | 2009-08-05 | 麻省理工学院 | Method for making high Jc superconducting films and polymer-nitrate solutions used therefore |
| CN101723659A (en) * | 2009-09-18 | 2010-06-09 | 西北有色金属研究院 | Method for preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal |
| CN102531567A (en) * | 2011-12-02 | 2012-07-04 | 西安理工大学 | Preparation method of high temperature superconductive film adopting modified low fluoride solution method |
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Patent Citations (3)
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| CN101501787A (en) * | 2006-07-17 | 2009-08-05 | 麻省理工学院 | Method for making high Jc superconducting films and polymer-nitrate solutions used therefore |
| CN101723659A (en) * | 2009-09-18 | 2010-06-09 | 西北有色金属研究院 | Method for preparing superconductive layer of coated conductor by organic deposition of low-fluorine metal |
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| W.CUI.ETAL: "YBa2Cu3O7−x Thin Films by Citrate-Based Non-fluorine precursor", 《J SUPERCOND NOV MAGN》 * |
| W.CUI.ETAL: "YBa2Cu3O7−x Thin Films by Citrate-Based Non-fluorine precursor", 《J SUPERCOND NOV MAGN》, no. 22, 9 July 2009 (2009-07-09), pages 811 - 815 * |
Cited By (1)
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| CN107311641A (en) * | 2017-07-25 | 2017-11-03 | 东北大学 | A kind of method that step Technology for Heating Processing prepares boron doped YBCO superconducting film |
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Application publication date: 20130828 |